Preparation of 1, 1-dicyano ethylene by the pyrolysis of 1-acetoxy-1, 1-dicyano ethane



Patented July 19, 1949 PREPARATION OF LI-DICYANO ETHYLENE BY THE PYROLYSIS I'ACETOXY-LI- DICYANO ETHANE Alan E. Ardis, Akron, Ohio, assignor to The B. F.

Goodrich Company, New York, N. Y., a corporation of New York No Drawing. Application November 12, 1947. Serial No. 785,520

9 Claims.

This invention relates to a method for the preparation of 1,1-dicyano ethylene which method involves the pyrolytic deacetoxylation of l-acetoxy-1,1dicyano ethane.

I have discovered that 1,1-dicyano ethylene may be readily prepared in good yields by the pyrolysis of 1-acetoxy-1,l-dicyano ethane. In addition to the 1,1-dicyano ethylene, some acetic acid is also formed.

The pyrolysis reaction proceeds substantially as follows:

CN H o CHz-QI O--CH; 2 6:4: n--t :on

(En I I N E This reaction provides a valuable and economical method for the preparation of 1,1-dicyano ethylene since the starting reactant, l-acetoxy- 1,1-dicyano ethane, is easily prepared by the dimerization of acetyl cyanide which in turn can be made from acetic anhydride and sodium cyanide or by the reaction of ketene and hydrogen cyanide.

The temperature at which the pyrolysis is conducted may be varied widely. Temperatures in the range of 400 to 750 C. are operative with the preferred range being from 600 to 650 C.

Increased yields of 1,1-dicyano ethylene are obtained when a substance is used to catalyze the pyrolysis. Among the materials which have been found useful in this connection are metallic chlorides, and especially chlorides of those metals occurring in Group II of the periodic table including beryllium, magnesium, calcium, zinc, strontium, cadmium and barium, with zinc chloride being the preferred catalyst. The amount of catalyst is not critical and may be varied considerably. For example, amounts of catalyst as low as one part by weight to eight parts or even more of 1-acetoxy-1,1-dicyano ethane and as high as one part or more of catalyst to one part of l-acetoxy-1,1-dicyano ethane may be used. The catalyst may be dispensed with entirely if desired and 1,1-dicyano ethylene still obtained.

The pyrolysis reaction can be conducted in several manners. The preferred method involves passing vapors of 1-acetoxy-1,1-dicyano ethane (a white solid melting at 70 C.) through a metal tube, preferably brass, which is connected to a receiver, preferably provided with external cooling means. Variations in this method involve the use of a glass pyrolysis tube instead of a. metal tube, or pyrolyzing the starting material over a hot resistance wire. The pyrolysis is preferably conducted at reduced pressures, especially from 2 2 to 50 mm., although pressures up to and including atmospheric pressure are operative.

The liquid product which collects in the receiver is a mixture of unreacted 1-acetoxy-l,1-dicyano ethane, acetic acid and 1,1-dicyano ethylene. The 1,1-dicyano ethylene is then separated from the mixture by utilizing any of several methods of separation. For example, one method of separating the 1,1-dicyano ethylene consists in utiliz ing the tendency of monomeric 1,1-dicyano ethylene to autopolymerize and allowing it to polymerize as it forms, or pouring the liquid product into water to hasten polymerization, after which the solid polymeric 1,1-dicyano ethylene can be easily separated from the liquid materials by liltration or decantation. The polymerized 1,1- dicyano ethylene can then be depolymerized by pyrolysis, preferably at temperatures of to 250 C., to obtain monomeric 1,1-dicyano ethylene.

A second useful method consists in extracting the 1,1-dicyano ethylene from the liquid mixture by use of a solvent, preferably one from which the l,l-dicyano ethylene will crystallize. This is done, for example, by mixing the liquid product and dry toluene or similar aromatic hydrocarbon, preferably in equal volumes, and cooling the mixture to a temperature of 20 C. or lower, whereupon monomeric 1,1-dicyano ethylene separates from the liquid mixture in form of crystals which are easily isolated as by filtration. The toluene layer is then decanted if desired and the supernatant liquid distilled to recover any uncrystallized monomer. High yields of very pure monomer are obtained by this method.

A third method involves treating the liquid product with a conjugated diolefin such as butadiene or cyclopentadiene which reacts with the 1,1-dicyano ethylene to form a solid substituted cyclohexene which can be separated from the acetic acid-and other impurities and pyrolyzed again at temperatures in excess of .400? C. to give monomeric 1,1-dicyano ethylene and the conjugated diolefin. Still a fourthmethod consists in distillation of the liquid product, preferably at reduced pressure, to obtain a fraction consisting substantially of 1,1-dicyano ethylene.

When using any of the latter three methods, it is desirable that the 1,1-dicyano ethylene be stabilized against polymerization from the time that it is formed. This may be accomplished by using a suitable 1,1-dicyano ethylene stabilizer (that is, a polymerization inhibitor) which may be mixed with the 1-acetoxy-1,1-dicyano ethane prior -to pyrolysis or placed in the receiver for the liquid pyrolysis product. Such a stabilizer is also prefterial.

erably present in the receiver used to collect the 1,1-dicyano ethylene when it is separated by distillation and when it is desired to obtain the monomer by pyrolysis of the polymer or the conjugated diolefin addition product. Suitable 1,1- dicyano ethylene stabilizers include phosphorus pentoxide and phosphorus pentasulfide, which are preferred, as well as antimony pentoxide, concentrated sulfuric acid and other materials reactive with water, since polymerization is catalyzed by even small amounts of hydroxyl ion. The stabilizer may be present in any desired amount but in general as little as 0.5 to 3.0% based on the amount of monomer is suiiicient to prevent polymerization for extended periods of time.

The following examples are intended to illustrate the preparation of 1.1- yano thylene by the method of this invention, but are not intended to limit the invention, for ther are, of course, numerous modifications. All parts are by weight.

Example I 80 parts of 1-ac'etoxy-1,1-dicyano ethane and 10 parts of zinc chloride are heated until vaporized and the vapors passed at 5 mm. pressure through a brass tube heated to a temperature of 560 C. 6'? parts of liquid product are collected in a receiver which is cooled in acetone-dry-ice bath. The liquid product is then distilled at a pressure of 5 mm. whereupon 18.5 parts (53% yield) of 1,1-dicyano ethylene, partly in the polymeric form, are obtained.

When this example is repeated in the absence of the zinc chloride catalyst, LI-dicyano ethylene is again obtained in yields which may be as high as 25%. Yields of 1,1-dicyano ethylene of about 20 to 50% are also secured when the zinc chloride of the example is replaced by other metal chlorides such as beryllium chloride which are volatile under the pyrolysis conditions.

Example II 80 parts of 1-acetoxy-l,l-dicyano ethane and parts of zinc chloride are heated and the vapors passed through a brass pyrolysis tube in combination with an ice-cooled receiver. The pyrolysis is conducted at a temperature of 675 C. and at a pressure of 7 mm. 54 parts of liquid product are collected. The liquid product is then poured into water whereupon the 1,1-dicyano ethylene polymerizes and the resulting solid polymer is separated by filtering. 25 parts (66%%) of 1,1-dicyano ethylene are obtained. The polymeric material may then be quantitatively converted into monomer by heating to 200 C.

Example III 40 parts of l-acetoxy-Ll-dicyano ethane and 40 parts of zinc chloride are heated and the vapors passed through a. brass pyrolysis tube which also contains brass chain packing. The pyrolysis tube is in combination with an ice-cooled receiver. A temperature of 670 C. and a pressure of 9 mm. is maintained throughout the reaction period. 34 parts of liquid product are collected in the receiver. The liquid product is then trac tionally distilled at a reflux ratio of 1:1 and 23 parts of a fraction consisting of 1,1 -dicyano ethylene are ,obtained. The 1,1'-dicyano ethylene is collected in the monomeric form but polymerizes rapidly on standing to a hard, clear ma- Emample IV 10 parts of 1-acetoxy-1,l-dicyano ethane and 10 parts of zinc chloride are pyrolyzed over a red hot nickel wire at a temperature of 600 C. and" to a solid material and is separated by filtering.

Upon further heating of the solid polymer at 200 C. in the presence of phosphorus pentoxide,

the 1,1-dicyano ethylene depolymerizes and 4 parts of monomeri 1,1-dicyano ethylene (M. P. 8 C.) are obtained.

Example V parts of 1-acetoxy-1,1-dicyano ethane, 20 parts zinc chloride, and 3 parts of phosphorus pentoxide are heated to a. temperature of 460 C. and a pressure of 7 mm. Pyrolysis occurs and 28 parts of liquid product are obtained. The liquid product is then added to 20 parts of butadiene and the mixture thus formed is placed in a sealed reaction tube for 20 hours at room temperature. The tube is then opened and the contents distilled at 450 G. into a receiver lined with phosphorus pentoxide. 10 parts of monomeric 1,1-dicyano ethylene (M. P. 8 0., N 1.4440) are obtained.

Example VI 80 parts of 1-acetoxy-1,1-dlcyano ethane and 40 parts of zinc chloride are heated and the vapors passed through a glass tube filled with ceramic packing and maintained at a temperature of 510 C. and a pressure of 15 mm. 50 parts of liquid product are collected. 28 parts of this liquid product are then treated as in Example II:

and a 44% yield of 1,1-dioyano ethylene is obtained.

Example VII 40 parts of 1-acetoxy-1,l-dicyano ethane and solution is then distilled to separate the acetic acid and unreacted 1-acetoxy-1,1-dicyano ethane.

23 parts of the polymerized 1,1-dicyano ethylene are recovered.

I Example VIII 80 parts of liquid product obtained as in Ex-- ample III are distilled to yield 24 parts of an intermediate fraction (N 1.430) which is mixed with an equal volume of dry tolueneand the mixture cooled to -25 C. Crystals of monomeric= 1,1-dicyano ethylene are formed and removed by filtering. The filtrate is decanted and distilled to recover uncrystallized 1,1-dicyano ethylene. 15

parts of monomeric 1,1-dicyano ethylene are obtained. I

1,1-dicyano ethylene prepared by the method of this invention is very valuable for the prepare-.-

tion of polymers and copolymers suitable as-synthetic rubbers, synthetic resins,- and plastics.

Furthermore, polymeric 1,1-dicyano ethylene and copolymers of 1,1-dicyano ethylene and other materials polymerizable therewith, may be spun into synthetic filaments which possess many valuable. properties including great tensile strength, fiex-.

ibility, and resistance to chemicals.

Numerous variations and modifications in the above procedure will be apparent to those skilled amaerc' in the art and are included within the scope of the invention as defined in the appended claims.

1. The method which comprises pyrolyzing 1-acetoxy-1,1-dicyano ethane at a temperature of 400 to 750 C. and separating 1,1-dicyano ethylene from the pyrolysis reaction mixture.

2. The method which comprises pyrolyzing 1-acetoxy-1,1-dicyano ethane at a temperature of 400 to 750 0., at a reduced pressure and in the presence of a chloride of a metallic element occurring in group 11 of the periodic table, and separating 1,1-dicyano ethylene from the pyrolysis reaction mixture.

3. The method which comprises pyrolyzing 1-acetoxy-1,1-dicyano ethane at a temperature of 400 to 750 C., at a pressure oi 5 to 50 mm. of Hg, and in the presence of zinc chloride and separating 1,1-dicyano ethylene from the pyrolysis reaction mixture.

4. The method which comprises pyrolyzing 1-acetoxy-1,1-dicyano ethane at a temperature of 600 C. to 650 C., at a pressure of 2 to 50 mm. of Hg. and in the presence of zinc chloride, and separating 1,1-dicyano ethylene from the pyrolysis reaction mixture.

5. The method which comprises pyrolyzing l-acetoxy-Ll-dicyano ethane at a temperature of 400 to 750 C., at a reduced pressure and in the presence of a chloride of a metallic element occurring in group II of the periodic table, collecting the pyrolysis reaction mixture in the presence of phosphorus pentoxide, and separating monomeric 1,1-dicyano ethylene from the pyrolysis reaction mixture.

6. The method which comprises pyrolyzing l-acetoxy-Ll-dicyano ethane at a temperature of 400 to 750 0., at a pressure of 2 to 50 mm. Hg., and in the presence of zinc chloride, collect ing the pyrolysis reaction mixture in the presence of phosphorus pentoxide, and separating mo-1 from the pyrolysis e pyrolysis reaction mixture in the presence of phosphorus pentoxide, and. separating mononeric 1,1-dicyano ethylene from the yrolysis reaction mixture.

8. The method which comprises pyrolyzing 1-acetoxy-1,1-dicyano ethane at a temperature of 400 to 750 C., at a pressure of 2 to mm.

mixture and heating the said polymerized 1,1-'

dicyano ethylene at a temperature of tc 250 C. in the presence of phosphorus pentoxide to obtain monomeric 1,1-dicyano ethylene.

9. The method which comprises ,pyrolyzing l-acetoxy-Ll-dicyano ethane at a temperature of 400 C. to 750 C., at a pressure of 2 to 50 mm. Hg. and in the presence of zinc chloride, collecting the pyrolysis reaction mixture inthe presence of phosphorus pentoxide, admixing the resulting pyrolysis mixture with toluene, cooling the re= suiting mixture to a temperature below -20 C. whereupon monomeric 1,1-dicyano ethylene separates from the liquid mixture in the form of crystals, and filtering said crystals of monomeric Ll-dicyano ethylene from the liquid mixture.

. ALAN E. ARDIS.

REFERENCES CITED The following references are of record in the file of this patent:

' UNITED STATES PATENTS 

